Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C313/00—Sulfinic acids; Sulfenic acids; Halides, esters or anhydrides thereof; Amides of sulfinic or sulfenic acids, i.e. compounds having singly-bound oxygen atoms of sulfinic or sulfenic groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
  • C07C313/02—Sulfinic acids; Derivatives thereof
  • C07C313/04—Sulfinic acids; Esters thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
  • C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
  • C07C17/275—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of hydrocarbons and halogenated hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
  • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
  • C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
  • C08F214/18—Monomers containing fluorine
  • C08F214/186—Monomers containing fluorine with non-fluorinated comonomers

Definitions

• the present disclosure relates to partially fluorinated sulfinic acids and salts thereof and methods of making.
• the monomers are added to a kettle along with an initiator, to initiate the polymerization, as well as a solvent, and in the case of aqueous emulsion polymerization, the polymerization is carried out in water and typically in the presence of an emulsifier in order to stabilize the emulsion.
• Fluorinated sulfinic acids and their salts have been used to initiate polymerization.
• the fluorinated sulfinic acids and their salts have been used along with oxidizing agents during polymerization of fluoromonomers as a means for achieving perfluorinated end groups, which may offer the advantages of more stability, improved performance, etc. by reducing or eliminating the less stable polar end-groups.
• the fluorinated sulfinic acid or salt thereof reacts with an oxidizing agent to generate a fluorinated alkyl radical via electron transfer, which then initiates the polymerization of monomers.
• novel compositions and methods of making which would enable the ability to change the molecular weight or architecture (e.g., linear or branch) of a polymer.
• novel compositions may improve the processing of fluoropolymer polymerization (e.g., by reducing processing step) and/or may improve the finished properties (performance, etc.) of a polymerized fluoropolymer.
• a composition according to formula I or its precursor, formula II is described herein.
• the present invention relates to a method comprising (a) reacting a terminal alkene compound with a halofluorosulfonylfluoride to produce a halohydrofluorosulfonylfluoride; (b) dehalohydrogenating the halohydrofluorosulfonylfluoride to produce an alkenefluorosulfonylfluoride; and (c) reducing of the alkenefluorosulfonylfluoride to produce an alkenefluorosulfinic acid or salt.
• Another method is described herein comprising (a) reacting a terminal alkene compound with a dihalofluorocarbon to produce a haloalkenefluorocarbon halide; (b) sulfonating the haloalkenefluorocarbon halide to produce a haloalkenefluorosulfinic acid or salt; and (c) dehalohydrogenating the haloalkenefluorosulfinic acid or salt to produce an alkenefluorosulfinic acid or salt.
• linking group refers to a divalent linking group.
• the linking group includes at least 1 carbon atom (in some embodiments, at least 2, 4, 8, 10, or even 20 carbon atoms).
• the linking group can be a linear or branched, cyclic or acyclic structure, that may be saturated or unsaturated, substituted or unsubstituted, and optionally contains one or more hetero-atoms selected from the group consisting of sulfur, oxygen, and nitrogen, and/or optionally contains one or more functional groups selected from the group consisting of ester, amide, sulfonamide, carbonyl, carbonate, urethane, urea, and carbamate.
• the linking group does not comprise a carbon atom and is a catenary heteroatom such as oxygen, sulfur, or nitrogen; and "perfluoroalkyl group as used herein, refers to a perfluorinated carbon group comprising that may be linear or branched and may comprise 2, 3, 4, 6, 8, 10 , 12, 18, or even 20 carbon atoms.
• At least one includes all numbers of one and greater (e.g., at least 2, at least 4, at least 6, at least 8, at least 10, at least 25, at least 50, at least 100, etc.).
• the present disclosure is directed to a novel monomer and its precursor. These compounds may be used in fluoropolymer polymerizations.
• CX 1 X 3 CX 2 -(R 1 ) p -CZ1Z2-SO 2 M (I) wherein X 1 , X 2 , and X 3 are independently selected from H, F, Cl, Br, I, CF 3 , and CH 3 , and wherein at least one of X 1 , X 2 , or X 3 is a H; R1 is a linking group; Z1 and Z2 are independently selected from F, Cl, I, Br, CF 3 , and a perfluoroalkyl group; p is 0 or 1; and M is a cation.
• R 1 may be non-fluorinated (no hydrogens are replaced by fluorine atoms), partially fluorinated (some of the hydrogens are replaced by fluorine atoms) or perfluorinated (all of the hydrogens are replaced by fluorine atoms).
• a hydrogen atom is replaced with a halogen other than fluorine, such as a chlorine, a bromine or an iodine atom, or a combination thereof.
• R 1 may or may not comprise double bonds.
• R 1 may be substituted or unsubstituted, linear or branched, cyclic or acyclic, and may optionally comprise a functional group (e.g., esters, ethers, ketones, amines, halides, etc.).
• a functional group e.g., esters, ethers, ketones, amines, halides, etc.
• R 1 is selected from: -(CH 2 ) a -, -(CF 2 ) a -, -(CF 2 ) a -O-(CF 2 ) b -, -(CF 2 ) a -[O-(CF 2 ) b ] c -, and -[(CF 2 ) a -O-] b -[(CF 2 ) c -O-] d , and combinations thereof, wherein a, b, c, and d are independently at least 1, 2, 3, 4, 10, 20, etc.
• R 1 is a perfluorinated group, optionally comprising heteroatoms, and X 1 , X 2 , and X 3 are all H.
• R 1 is a catenary heteroatom such as oxygen, sulfur, or nitrogen.
• M in formula I may comprise H + , an inorganic cation including, but not limited to: Na + , Li + , Cs + , Ca +2 , K + , NH 4 + , Mg +2 , Zn +2 , and Cu +2 , and/or an organic cation including, but not limited to N(CH 3 ) 4 + , NH 2 (CH 3 ) 2 + , N(CH 2 CH 3 ) 4 + , NH(CH 2 CH 3 ) 3 + , NH(CH 3 ) 3 + , and ((CH 3 CH 2 CH 2 CH 2 ) 4 )P + .
• an inorganic cation including, but not limited to: Na + , Li + , Cs + , Ca +2 , K + , NH 4 + , Mg +2 , Zn +2 , and Cu +2
• an organic cation including, but not limited to N(CH 3 ) 4 + , NH 2 (CH 3 ) 2
• the monomer according to formula I may be prepared by Method I or Method II as disclosed below.
• a precursor to the monomer of formula I is shown in formula II: CX 4 X 1 X 3 -CX 5 X 2 -(R 1 ) p -CZ1Z2-SO 2 M (II) wherein X 1 , X 2 , and X 3 are independently selected from H, F, Cl, Br, I, CF 3 or CH 3 , wherein at least one of X 1 , X 2 , or X 3 is a H, and X 4 and X 5 are independently selected from H, F, Cl, Br and I; R 1 is a linking group; Z1 and Z2 are independently selected from F, Cl, I, Br, CF 3 , and a perfluoroalkyl group, p is 0 or 1; and M is selected from F and a cation.
• R 1 may be non-fluorinated, partially fluorinated, or perfluorinated.
• the hydrogen atoms are replaced with a halogen other than fluorine, such as a chlorine, a bromine or a iodine atom, or a combination thereof.
• R 1 may or may not comprise double bonds.
• R 1 may be substituted or unsubstituted, linear or branched, cyclic or acyclic, and may optionally comprise a functional group (e.g., esters, ethers, ketones, amines, halides, etc.).
• R 1 is a perfluorinated group, optionally comprising a heteroatom, and X 1 , X 2 , and X 3 are all H.
• R 1 is a catenary heteroatom such as oxygen, sulfur, or nitrogen.
• M in formula I may comprise F, H + , an inorganic cation including, but not limited to: Na + , Li + , Cs + , Ca +2 , K + , NH 4 + , Mg +2 , Zn +2 , and Cu +2 and/or an organic cation including, but not limited to N(CH 3 ) 4 + , NH 2 (CH 3 ) 2 + , N(CH 2 CH 3 ) 4 + , NH(CH 2 CH 3 ) 3 + , NH(CH 3 ) 3 + , and ((CH 3 CH 2 CH 2 CH 2 ) 4 )P + .
• an inorganic cation including, but not limited to: Na + , Li + , Cs + , Ca +2 , K + , NH 4 + , Mg +2 , Zn +2 , and Cu +2 and/or an organic cation including, but not limited to N(CH 3 ) 4 + , NH 2 (CH 3 )
• the monomer according to formula I includes: XCH 2 CH 2 -(CF 2 ) n -SO 2 M (IIa), where M is defined as above; X is selected from H, F, Cl, Br, I, CF 3 or CH 3 ; and n is at least 1, 2, 4, 6, 10, 20, etc.
• the monomer according to formula I includes: XCH 2 -CH 2 -(CF 2 ) 2 O(CF 2 ) 2 -SO 2 M (IIb) where M is F or a cation and X is selected from F, Cl, Br, and I.
• the precursor shown in Formula II is obtained during the process as disclosed in Method II below.
• Method I a terminal alkene compound and a halofluorosulfonylfluoride are reacted together to produce a halohydrofluorosulfonylfluoride.
• the halohydrofluorosulfonylfluoride is then dehalohydrogenated to produce an alkenefluorosulfonylfluoride.
• the alkenefluorosulfonylfluoride is reduced to produce an alkenefluorosulfinic acid or salt.
• the terminal alkene compound of the present disclosure comprises a terminal carbon-carbon double bond with at least one hydrogen off of the carbon double bond.
• the halofluorosulfonylfluoride of the present disclosure is a ⁇ - halofluorosulfonylfluoride (i.e., a terminal sulfonyl fluoride).
• the halofluorosulfonylfluoride comprises a compound of the general formula III: X 5 (R 1 ) p -CZ1Z2-SO 2 F (III) where X 5 is selected from Br, I, and Cl; R 1 is a linking group as described above; Z1 and Z2 are independently selected from F, Cl, Br, CF 3 and a perfluoroalkyl group; and p is 0 or 1.
• Exemplary halofluorosulfonylfluorides include: ICF 2 CF 2 -O-CF 2 CF 2 SO 2 F, ICF 2 CF 2 CF 2 -O-CF 2 CF 2 SO 2 F, I(CF 2 ) 4 SO 2 F, I(CF 2 ) 3 SO 2 F, I(CF 2 ) 5 SO 2 F, I(CF 2 ) 6 SO 2 F, BrCF 2 SO 2 F, BrCF 2 CF 2 CF 2 -O-CF 2 CF 2 SO 2 F, BrCF 2 CF 2 CF 2 CF 2 -O-CF 2 CF 2 SO 2 F, Br(CF 2 ) 4 SO 2 F, Br(CF 2 ) 3 SO 2 F, Br(CF 2 ) 5 SO 2 F, Br(CF 2 ) 6 SO 2 F, ICF 2 SO 2 F, and BrCF 2 SO 2 F.
• the reaction between the terminal alkene compound and the halofluorosulfonylfluoride is initiated thermally, by photo-irradiation, or in the presence of an initiator, or a combination thereof.
• the reaction between the terminal alkene compound and the halofluorosulfonylfluoride may be conducted at a temperature of between at least 10, 20, 25, 30, or even 35°C; at most 90, 100, 150, 200 or even 220°C.
• the reaction between the terminal alkene compound and the halofluorosulfonylfluoride may be conducted using photo-irradiation e.g., ultra-violet radiation.
• exemplary initiators include: a peroxide, a diazo compound, and single electron donor, such as a metal or metal complex, and redox system for radical reaction of fluorinated iodide.
• the reaction between the terminal alkene compound and the halofluorosulfonylfluoride is conducted in the absence of solvent. Eliminating the solvent may reduce processing costs associated with buying and disposing of the solvent.
• first solvents include: a perfluorinated solvent, such as perfluoromorpholine, and a partially fluorinated solvent, such as C 4 F 9 OCH 3 and C 4 F 9 OCH 2 CH 3 .
• the ratio of terminal alkene compound to the halofluorosulfonylfluoride to produce the halohydrofluorosulfonylfluoride is at least 1 to 1, or even 2:1. Preferably there is an excess of terminal alkene compound in the addition reaction.
• the halohydrofluorosulfonylfluoride produced (e.g., (a) above) is then dehalohydrogenated (loss of a halohydrogen, e.g., HI) to produce an alkenefluorosulfonylfluoride.
• the alkenefluorosulfonylfluoride comprises a fluorinated carbon group linking a terminal double bond and a terminal sulfonyl fluoride group such as shown in (b).
• the dehalohydrogenating may be conducted in the presence of a base.
• exemplary bases include: 1,8-diazobicyclo[5,4,0]undec-7-ene (DBU), triethylamine, and tributyl amine.
• DBU 1,8-diazobicyclo[5,4,0]undec-7-ene
• the base should be selected such that the sufonyl fluoride of the starting material is not hydrolyzed.
• the dehalohydrogenating reaction may be conducted at a temperature of between at least 10, 20, 25, 30, or even 35°C; at most 60, 70, 80, or even 90°C.
• the ratio of base to halohydrofluorosulfonylfluoride is at least 1 to 1, or even 2:1. Preferably there is an excess of base.
• dehalohydrogenating reaction is conducted in the presence of a solvent.
• solvents include, ethers, alcohols, etc.
• the alkenefluorosulfonylfluoride is reduced to produce the monomer according to formula I, an alkenefluorosulfinic acid or salt (e.g., (c) above).
• the reducing step may be done in the presence of a reducing agent and a second solvent.
• the selection of the second solvent may depend on the reducing agent used.
• Exemplary second solvents include, ethers (such as dialkyl ethers (e.g., diethyl ether), CH 3 OCH 2 CH 2 OCH 3 , t-butyl methyl ether, glycol dialkyl ether, dioxane, and tetrahydrofuran), alcohols, acetonitrile, water, and combinations thereof.
• Hydride reducing agents useful in the present disclosure include those represented by the formula, M'LH 4 , wherein M' is an alkali metal or an alkaline Earth metal and L is Aluminum or Boron, including, for example, sodium borohydride, sodium cyanoborohydride, potassium borohydride, lithium borohydride, and lithium aluminum hydride.
• Useful hydride reducing agents also include those represented by the formula, M"H n , wherein M" is an alkali metal, and n is an integer selected from 1 or 2, including, for example, sodium hydride, lithium hydride, potassium hydride, barium hydride, and calcium hydride.
• hydride reducing agents include mono-, di-, or tri(lower alkoxy) alkali metal aluminum hydrides, mono-, di-, or tri-(lower alkoxy lower alkoxy) alkali metal aluminum hydrides, di(lower alkyl) aluminum hydrides, alkalimetalcyanoborohydrides, tri(loweralkyl) tin hydrides, tri(aryl) tin hydrides, Li(C 2 H 5 ) 3 BH, and (((CH 3 ) 2 CHCH 2 ) 2 AlH) 2 .
• Another useful reducing agent is a sulfite such as-CF 2 SO 2 F or -CF 2 SO 2 M, including K 2 SO 3 , Na 2 SO 3 , KHSO 3 and NaHSO 3 .
• a terminal alkene compound is reacted with a dihalofluorocarbon to produce a haloalkanefluorocarbon halide.
• the haloalkanefluorocarbon halide is then sulfinated to produce a haloalkenefluorosulfinic acid or salt.
• the haloalkenefluorosulfinic acid or salt is dehalohydrogenated to produce an alkenefluorosulfinic acid or salt.
• the terminal alkene compound of the present disclosure comprises a terminal carbon-carbon double bond with at least one hydrogen off of the carbon double bond.
• the dihalofluorocarbon of the present disclosure comprises the general formula IV: X 6 -(R 1 ) p -CZ1 Z2-X 7 wherein X 6 and X 7 are independently selected from Cl, Br, and I; R 1 is a linking group as described above; Z1 and Z2 are independently selected from F, Cl, Br, CF 3 and a perfluoroalkyl group; p is 0 or 1.
• Reacting the terminal alkene compound and the dihalofluorocarbon together produce a haloalkenefluorocarbon halide (e.g., (d) above).
• the reaction may be conducted at a temperature of between at least 10, 20, 25, 30, or even 35°C; at most 90, 100, 150, 200 or even 220°C.
• the reaction between the terminal alkene compound and the dihalofluorocarbon is initiated in the presence of an initiator.
• Initiators as known in the art may be used including peroxides, diazo compounds, metals, and combinations thereof.
• Exemplary peroxide initiators include: diisobutyryl peroxide (available under the trade designation "TRIGONOX 187-C30" from AkzoNobel, Amsterdam), cumyl peroxyneodecanoate (available under the trade designation "TRIGONOX 99-C75" from AkzoNobel), peroxydicarbonate (available under the trade designation "TRIGONOX ADC” from AkzoNobel), t-butyl peroxyneodecanoate (available under the trade designation "TRIGONOX 23" from AkzoNobel), dibenzoyl peroxide, di-t-butyl peroxide, and t-butyl cumyl peroxide.
• Exemplary a diazo compound initiators include: 2,2'-Azobis(2-methylbutyronitrile) (available under the trade designation "VAZO 67" from E.I. du Pont de Nemours & Co, Wilmington, DE) and 2,2'-azobis(isobutyronitrile).
• Exemplary metal initiators include: Zn, Mg, Ni and Cu or metal complexes such as Pd(PPh 3 ) 4 , Pt(PPh 3 ) 4 , Pb(OAc) 4 and RhCl(PPh 3 ) 3 .
• haloalkenefluorocarbon halide produced is then sulfonated to produce the precursor according to formula II, a haloalkenefluorosulfinic acid or salt (see (e) above).
• a sulfinating system is used to dehalosulfinate (i.e., remove a halogen and sulfinate the compound) the haloalkenefluorocarbon halide. Sulfinating systems are known to those skilled in the art.
• Exemplary sulfinating system include, Na 2 S 2 O 4 , NaHSO 3 /(NH 4 ) 2 Ce(NO 3 ) 6 , NaHSO 3 /FeCl 3 , NaHSO 3 /K 3 [Fe(CN) 6 ], HOCH 2 SO 2 Na, and (NH 2 ) 2 CSO 2 , Na 2 S 2 O 5, and combinations thereof.
• the haloalkenefluorosulfinic acid or salt then is dehalohydrogenated to produce produce the monomer according to formula I, an alkenefluorosulfinic acid or salt (e.g., (f) above).
• the dehalohydrogenating may be conducted in the presence of a base.
• exemplary bases include: KOH, NaOH, LiOH, Na 2 CO 3 , NaHCO 3 , K 2 CO 3 , 1,8-diazobicyclo[5,4,0]undec-7-ene (DBU), and combinations thereof.
• the dehalohydrogenating reaction may be conducted at a temperature of between at least 10, 20, 25, 30, or even 35°C; at most 60, 70, 80, or even 90°C.
• the ratio of base to the haloalkenefluorosulfinic acid or salt thereof is at least 1 to 1, or even 2:1. Preferably there is an excess of base.
• dehalohydrogenating reaction is conducted in the presence of a solvent.
• solvents include, water, alcohol, and combinations thereof.
• the monomer according to formula I and/or the precursor according formula II may be isolated and purified by known methods.
• the crude product is isolated from the reaction mixture by filtration to remove insoluble inorganic salts, then rotary evaporation to remove solvent to give sulfinate salt solid.
• the crude solid is purified by extracting with warm alcohol, such as isopropanol to remove insoluble inorganic impurity followed by the stripping out of solvent.
• a concentrated acid such as, for example, sulfuric acid, is added to protonate the sulfinate salt resulting in a phase split.
• the crude product is isolated by the addition of an acid, such as, for example, sulfuric acid, followed by extraction with an organic solvent, such as t-butyl methyl ether and diethyl ether.
• an acid such as, for example, sulfuric acid
• organic solvent such as t-butyl methyl ether and diethyl ether.
• the desired product in acid form then is isolated by removal of the organic solvent.
• further purification of the crude product is sometimes not necessary.
• the elimination of the purification step may reduce processing time and cost.
• the reaction mixture or crude product may be purified, for example, by repeated recrystallization.
• the monomer according to formula I may be useful as a surfactant (emulsifier), a dispersion stabilizer, or an initiator.
• the monomer according to formula I may be useful as an initiator for polymers having fewer undesired end-polar groups, or as a polymerizable surfactant, thus eliminating the need to remove the surfactant post-polymerization.
• the monomer of the present disclosure may be used in polymerizations of fluoropolymers. Because one end of the monomer according to formula I comprises a double bond, the monomer may be used in polymerization reactions. Because the other end of the monomer according to formula I comprises a sulfinic acid or salt thereof, this site is able to form a radical and act as an initiator in polymerization reactions. Therefore, the monomer according to formula I may be consumed during a polymerization. Furthermore, because of the sulfinic acid end group, polymers made using this initiator may have reduced or no amounts of polar end-groups, which may aid in stability of the polymer.
• DBU 1,8-diazabicycloundec-7-ene Commercially available Aldrich THF Tetrahydrofuran, available from EMD Chemicals Inc. OmniSolv, Gibbstown, NJ NaBH 4 Available from Sigma-Aldrich Chemical Co. I(CF 2 ) 4 I Available from Shanghai FWD Chemicals Limited, Shanghai 200237, China Initiator Available under the trade designation "VAZO-67" from E.I. du Pont de Nemours & Co, Wilmington, DE Hexane Available from EMD Chemicals, Inc. CH 3 CN Available from Sigma-Aldrich Chemical Co. Na 2 S 2 O 4 Available from J.T. Baker, Avantor Performance Materials, Inc., Phillipsburg, NJ KOH Available from Sigma-Aldrich Chemical Co. t-BuOMe t-butyl methyl ether, available from EMD Chemicals, Inc.
• the filtered solution showed two phases, and only top phase showed fluorinated product based on 19 F NMR analysis.
• the top phase was separated, and the solvents were removed by rotary evaporation to give 76.5g wet solid.
• the wet solid was dissolved in water and the following chemical shifts were recorded, -115 (dxt), -122 (m), -124 (m) and -130 (dxt) ppm.
• No effect on ICH 2 CH 2 - was observed during the dehalosulfination based 1 H NMR analysis (2.5-3 ppm multiplet for -CH 2 I and 3.2 ppm (txm) for -CH 2 CF 2 -).

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